Synthesis and Properties of Carborane-Appended ... - ACS Publications

Apr 16, 2010 - Barada Prasanna Dash, Rashmirekha Satapathy, Elizabeth R. Gaillard, John A. Maguire and Narayan S. Hosmane*. Department of Chemistry ...
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Synthesis and Properties of Carborane-Appended C3-Symmetrical Extended π Systems Barada Prasanna Dash,† Rashmirekha Satapathy,† Elizabeth R. Gaillard,† John A. Maguire,‡ and Narayan S. Hosmane*,† Department of Chemistry and Biochemistry, Northern Illinois UniVersity, DeKalb, Illinois 60115-2862, and Department of Chemistry, Southern Methodist UniVersity, Dallas, Texas 75275-0314 Received March 4, 2010; E-mail: [email protected]

Abstract: A series of C3-symmetric π-conjugated compounds containing three to six o-carborane clusters have been synthesized by employing palladium-catalyzed Suzuki coupling reactions and palladium-catalyzed acetylation reactions, followed by silicon tetrachloride mediated trimerization reactions. Carborane-containing extended trimers were found to emit blue light. Incorporation of o-carborane clusters into extended π-conjugated systems led to 22-70% enhancement of their relative fluorescence quantum yields. Decapitation of o-carborane clusters made these extended trimers water soluble, and their aqueous solutions were also found to be fluorescent, but with a reduced fluorescence intensity. The carborane-appended π-conjugated compounds are found to be extremely thermally stable, and for some of these compounds only 10% mass loss occurred at temperatures close to 500 °C. The DSC thermograms of smaller Ccageappended trimers indicate the occurrence of solid-solid phase transitions.

Introduction

The synthesis of dendritic and symmetrical star-shaped π-conjugated compounds and the study of their physical properties are of intense current scientific interest. These classes of compounds find a number of important applications,1 including use as organic light-emitting materials,2 liquidcrystalline materials,3 effective drug delivery agents,4 and highly efficient catalysts.5 Some of the very exciting applications of such macromolecular compounds include their self-assembly †

Northern Illinois University. Southern Methodist University. (1) For reviews see: (a) Northrop, B. H.; Zheng, Y.-R.; Chi, K.-W.; Stang, P. J. Acc. Chem. Res. 2009, 42, 1554–1563. (b) Saragi, T. P. I.; Spehr, T.; Siebert, A.; Fuhrman-Lieker, T.; Salbeck, J. Chem. ReV. 2007, 107, 1011–1065. (c) Lo, S.-C.; Burn, P. L. Chem. ReV. 2007, 107, 1097– 1116. (d) Hoeben, F. J. M.; Jonkheijm, P.; Meijer, E. W.; Schenning, A. P. H. J. Chem. ReV. 2005, 105, 1491–1546. (e) Grayson, S. M.; Frechet, J. M. J. Chem. ReV. 2001, 101, 3819–3867. (2) (a) Laquai, F.; Mishra, A. K.; Ribas, M. R.; Petrozza, A.; Jacob, J.; Akcelrud, L.; Mullen, K.; Friend, R. H.; Wegner, G. AdV. Funct. Mater. 2007, 17, 3231–3240. (b) Watson, M. D.; Jackel, F.; Severin, N.; Rabe, J. P.; Mullen, K. J. Am. Chem. Soc. 2004, 126, 1402–1407. (c) Vijaylakshmi, N.; Maitra, U. Org. Lett. 2005, 7, 2727–2730. (d) Weil, T.; Reuther, E.; Mullen, K. Angew. Chem., Int. Ed. 2002, 41, 1900– 1904. (3) (a) Kumar, S. Chem. Soc. ReV. 2006, 35, 83–109. (b) Pisula, W.; Kastler, M.; Wasserfallen, D.; Pakula, T.; Mullen, K. J. Am. Chem. Soc. 2004, 126, 8074–8075. (c) Craats, A. M. V.; Warman, J. M.; Fechtenkotter, A.; Brand, J. D.; Harbison, M. A.; Mullen, K. AdV. Mater. 1999, 11, 1469–1472. (d) Muller, G. R. G.; Meiners, C.; Enkelmann, V.; Geerts, Y.; Mullen, K. J. Mater. Chem. 1998, 1, 61– 64. (4) (a) Fox, M. E.; Szoka, F. C.; Frechet, J. M. J. Acc. Chem. Res. 2009, 42, 1141–1151. (b) Almutairi, A.; Rossin, R.; Shokeen, M.; Hangooly, A.; Ananth, A.; Capoccia, B.; Guillaudeu, S.; Abendschein, D.; Welch, M. J.; Frechet, J. M. J. Proc. Natl. Acad. Sci. U.S.A. 2009, 685–690. (c) Nishimaya, N.; Iriyama, A.; Jang, W.-D.; Miyata, K.; Itaka, K.; Inoue, Y.; Takahashi, H.; Yanagi, Y.; Tamaki, Y.; Koyama, H.; Kataoka, K. Nat. Mater. 2005, 934–941. ‡

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and the aggregation leading to highly ordered nanostructured materials.6 In a parallel development, it has been found that icosahedral carborane clusters are versatile synthetic building blocks and have been used in materials science, medicine, and catalysis.7 Specifically, icosahedral carborane clusters are thermally very stable and easy to functionalize.8 Current investigations in our laboratory to incorporate readily available o-carboranes into π-conjugated symmetrical structures have resulted in hybrid compounds of dramatically high thermal stability.9 Metalated carborane-containing macrocycles show properties such as self-assembly which could make them useful in the promising field of nanoscience.10 It has also been found that o-carborane clusters can readily be functionalized at both boron and carbon atoms of the cluster.11 The electron-rich B9 (5) (a) Astruc, D.; Orneals, C.; Ruiz, J. Acc. Chem. Res. 2008, 41, 841– 856. (b) Chi, Y.; Scroggins, S. T.; Boz, E.; Frechet, J. M. J. J. Am. Chem. Soc. 2008, 130, 17287–117289. (c) Lemo, J.; Heuze, K.; Astruc, D. Chem. Commun. 1999, 4351–4353. (6) (a) Kraft, M. L.; Moore, J. F. Science 2008, 320, 620–621. (b) Zang, L.; Che, Y.; Moore, J. F. Acc. Chem. Res. 2008, 41, 1596–1608. (c) Li, S. S.; Northrop, B. H.; Yuan, Q.-H.; Wan, L.-J.; Stang, P. J. Acc. Chem. Res. 2009, 42, 249–259. (d) Zheng, Y.-R.; Yang, H. B.; Ghosh, K.; Zhao, L.; Stang, P. J. Chem. Eur. J. 2009, 15, 7203–7214. (e) Northrop, B. H.; Yang, H.-B.; Stang, P. J. Chem. Commun. 2008, 5896–5908. (f) Ghosh, K.; Hu, J.; White, H. S.; Stang, P. J. J. Am. Chem. Soc. 2009, 131, 6695–6697. (g) Lee, J.; Ghosh, K.; Stang, P. J. J. Am. Chem. Soc. 2009, 131, 12028–12029. (7) For reviews see: (a) Zhu, Y.; Cheng, K. Y.; Maguire, J. A.; Hosmane, N. S. Curr. Chem. Biol. 2007, 1, 141–149. (b) Grimes, R. N. J. Chem. Educ. 2004, 81, 658–672. (c) Plesek, J. Chem. ReV. 1992, 92, 269– 278. (d) Hawthorne, M. F.; Maderna, A. Chem. ReV. 1999, 99, 3421– 3434. (e) Teixidor, F.; Vinas, C.; Demonceau, A.; Nunez, R. Pure Appl. Chem. 2003, 75, 1305–1313. (8) Valliant, J. F.; Guenther, K. J.; Arienne, S.; King, S.; Morel, P.; Schaffer, P.; Sogbein, O. O.; Stephenson, K. A. Coord. Chem. ReV. 2002, 232, 173–230. (9) Dash, B. P.; Satapathy, R.; Maguire, J. A.; Hosmane, N. S. Chem. Commun. 2009, 3267–3269. 10.1021/ja101845m  2010 American Chemical Society

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Figure 1. Structure of the Bcage-appended trimer.

boron atom of the o-carborane clusters can undergo facile Friedel-Craft type electrophilic substitution reactions to generate B9-substituted products. Carboranyl aromatic ketones attached to this boron atom of the cluster were synthesized and were found to undergo trimerization in the presence of a silicon tetrachloride/ethanol mediated reaction to generate C3-symmetrical trimers having three carborane clusters in the periphery, as shown in Figure 1.11 Because of the acidic nature of the cage hydrogens, these o-carborane clusters can also undergo facile functionalization at the cage carbon to produce Ccage-appended extended trimers. Herein we describe the syntheses of a number of Ccage-appended C3-symmetrical trimers, incorporating ocarborane clusters. We also report on the relative thermal stabilities of Bcage- and Ccage-appended trimers, as well as the effect of carboranes on the photophysical properties of extended trimers. The deboronation of the attached o-carborane clusters led to the formation of the respective water-soluble compounds,12 whose spectroscopic properties are also reported.

Scheme 2. Synthesis of Ccage-Appended Extended Trimers

Containing Three o-Carborane Clusters

Results and Discussion

The carborane Ccage-appended C3-symmetric trimers containing three to six o-carborane clusters were synthesized by employing Suzuki coupling reactions and palladium-catalyzed acetylation reactions,13 followed by SiCl4/ethanol mediated trimerizations11,14 of the so formed carborane-appended aryl ketones, as shown in Schemes 1-3. Suzuki coupling reactions were generally carried out using the common palladium catalyst PdCl2(PPh3)2 and K2CO3 as a base. Solubility difficulties of the aryl ketones in the trimerization reactions were solved by using as the solvent a mixture of toluene and ethanol in a 1:3 proportion. Smaller trimers could be obtained with roomtemperature reactions, but for the extended trimers an elevated temperature of between 40-50 °C was required. Synthesis of Trimers. The syntheses of the carborane Ccageappended conjugated systems, containing three carborane (10) (a) Jude, H.; Disteldorf, H.; Fischer, S.; Wedge, T.; Hawkridge, A. M.; Arif, A. M.; Hawthorne, F.; Muddiman, D. C.; Stang, P. J. J. Am. Chem. Soc. 2005, 127, 12131–12139. (b) Das, N.; Stang, P. J.; Arif, A. M.; Campana, C. F. J. Org. Chem. 2005, 70, 10440–10446. (11) Dash, B. P.; Satapathy, R.; Maguire, J. A.; Hosmane, N. S. Org. Lett. 2008, 10, 2247–2250, and references therein. (12) (a) Vyakaranam, K.; Rana, G.; Ratanasuwan, A.; Hosmane, S. N.; Maguire, J. A.; Hosmane, N. S. Organometallics 2002, 21, 3905– 3912. (b) Yoo, J.; Hwang, J.-W.; Do, Y. Inorg. Chem. 2001, 40, 568– 570. (c) Gonzalez-Campo, A.; Vinas, C.; Teixidor, F.; Nunez, R.; Sillanpaa, R.; Kivekas, R. Macromolecules 2007, 40, 5644–5652. (13) Cacchi, S.; Fabrizi, G.; Gavazza, F.; Goggiamani, A. Org. Lett. 2003, 5, 289–291. (14) (a) Bao, C.; Lu, R.; Jin, M.; Xue, P.; Tan, C.; Xu, T.; Liu, G.; Zhao, Y. Chem. Eur. J. 2006, 12, 3287–3294. (b) Yang, J.-X.; Tao, X.-T.; Yuan, C. X.; Yan, Y. X.; Wang, L.; Liu, Z.; Ren, Y.; Jiang, M. H. J. Am. Chem. Soc. 2005, 127, 3278–3279. (c) Cao, X.-Y.; Liu, X.-H.; Zhou, X.-H.; Zhang, Y.; Jiang, Y.; Cao, Y.; Cui, Y.-X.; Pei, J. J. Org. Chem. 2004, 69, 6050–6058.

clusters, are outlined in Schemes 1 and 2. Compound 2 was prepared from the lithiated 1-methyl-o-carborane and 4-iodobenzyl bromide in DME and was used as the starting compound.15 A Suzuki coupling reaction of compound 2 with (4acetylphenyl)boronic acid in the presence of catalytic amounts of water produced the desired carborane-appended aryl ketone 3 in good yield. Ketone 3 then underwent trimerization in the presence of SiCl4/ethanol to produce the extended trimer 6, in 61% yield. Palladium-catalyzed acetylation13 of 2 worked well to produce the desired carborane-appended aryl ketone 4, which (15) Vicente, H.; Edwards, F.; Shetty, S. J.; Hou, Y.; Boggan, J. E. Bioorg. Med. Chem. 2002, 10, 481–492. J. AM. CHEM. SOC.

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Scheme 3. Synthesis of Ccage-Appended Trimers Containing Six o-Carborane Clusters

was then trimerized with SiCl4/ethanol to produce trimer 5 (Scheme 1). A more extended version of the trimers, compound 10, was prepared from the precursor ketone 9 via another SiCl4/ ethanol mediated trimerization reaction in about 30% yield. The intermediate ketone 9 was obtained via a Suzuki coupling between carborane-appended boronic acid 716 and commercially available 4′-(4-bromophenyl)acetophenone 8 (Scheme 2). To further increase the number of carborane clusters around the 1,3,5-phenylene core, we started from the commercially available 3,5-dimethyl-1-iodobenzene (11), which underwent radical bromination in the presence of N-bromosuccinimide and the radical initiator AIBN to give compound 12 (Scheme 3). Two equivalents of lithiated 1-methyl-o-carborane in the presence of a catalytic amount of lithium iodide produced the key intermediate 13 in good yield, at room temperature. A Suzuki coupling of 13 with (4-acetylphenyl)boronic acid or a palladiumcatalyzed acetylation produced the desired ketones 14 and 16, respectively. Trimerizations of the ketones led to the respective products 15 and 17, having six o-carborane clusters, as shown in Scheme 3. A general synthetic route to functionalized Ccage-appended trimers is shown in Scheme 4. One of the acidic hydrogens on the o-carborane was protected by the bulky TBDMS group, following a literature procedure.17 The TBDMS-protected o-carborane 18 could be lithiated and then treated with an iodo (16) Hao, E.; Fabre, B.; Fronczeka, F. R.; Vicente, M. G. H. Chem. Mater. 2007, 19, 6195–6205. (17) Gomez, F. A.; Hawthorne, M. F. J. Org. Chem. 1992, 57, 1384–1390. 6580

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Scheme 4. Synthesis of Substituted Ccage-Appended Trimers

Scheme 5. Deboronation of o-Carborane Clusters in Trimers

compound, in this case 1-iodoheptane, to produce the Ccageheptyl-substituted carborane 19. After deprotection of the TBDMS group with TBAF, the resulting compound 20 was then treated with 4-iodobenzyl bromide in the presence of BuLi in DME to give 21, which upon palladium-catalyzed acetylation led to the desired heptyl-substituted carboranyl ketone 22. Trimerization of this ketone led to the heptyl-substituted carboranyl trimer 23 in good yield (Scheme 4). Water-Soluble Trimers. The decapitation reaction of ocarboranes by alcoholic NaOH leads to the removal of one of the vertex boron atoms to give monoanionic nido-carborane

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Figure 2. Water-soluble trimers.

Figure 3. C3-symmetric phenylene cores. Figure 4. (A) Absorption and emission spectra of trimers in dichlo-

species. The monoanions can be further deprotonated to give dianions, which can act as ligands for different metals.18 It was found that all of the carboranes of the trimers 5, 6, 10, 15, and 17 could be decapitated to give the corresponding water-soluble compounds. Scheme 5 shows a typical decapitation reaction of 6 to give 24. The two other extended trimers, 15 and 10, underwent similar deboronation reactions that led to the corresponding water-soluble trimers 25 and 26, respectively (Figure 2). The spectroscopic properties of these trimers were later evaluated in water. Controls. The control trimers A and B (Figure 3) without any carboranes were also synthesized. Control A was prepared by the SiCl4/ethanol mediated trimerization of acetophenone, whereas the extended control B was prepared via a Suzuki coupling reaction of commercially available 1,3,5-tris(4-iodophenyl)benzene with phenylboronic acid (see the Supporting Information).19 Photophysical Properties. Symmetrical 1,3,5-phenylenebenzene core based structures, shown in Figure 3, have been used as photostable chromophores for light-emitting materials.20 Specifically, the extended versions such as 1,3,5-tris(p-oligophenylene)benzenes (B) were found to be blue-violet light emitting and therefore useful as hole-blocking molecular materials21a and UV-laser dyes.21b However, the low solubility of such symmetrical polycyclic aromatic compounds in polar solvents was considered as a primary drawback for their general use as laser dyes.21b,22 The effect of carboranes on the photophysical properties of polycyclic compounds was studied by comparing the spectroscopic properties of dichloromethane solutions of the carborane-appended extended trimers 6, 10, and 15 with B (see (18) (a) Deng, L.; Xie, Z. Organometallics 2007, 26, 1832–1845. (b) Xie, Z. Coord. Chem. ReV. 2006, 250, 259–272. (c) Hosmane, N. S.; Maguire, J. A. Organometallics 2005, 24, 1356–1389. (d) Hawthorne, M. F.; Young, D. C.; Garrett, D. A.; Owen, D. A.; Schwerin, S. G.; Tebbe, F. N.; Wegner, P. A. J. Am. Chem. Soc. 1968, 90, 862–868. (e) Hawthorne, M. F.; Young, D. C.; Andrews, T. D.; Howe, D. V.; Pilling, R. L.; Pitts, A. D.; Reintjes, M.; Warren, L. F.; Wegner, P. A. J. Am. Chem. Soc. 1968, 90, 879–896. (19) Kotha, S.; Kasinath, D.; Lahiri, K.; Sunoj, R.B. Eur. J. Org. Chem. 2004, 4003–4013.

romethane: (red) 10; (blue) 15; (orange) 6; (green) control B. (B) Absorption and emission spectra of water-soluble trimers in water: (red) 26; (orange) 24; (blue) 25. For compound 26 Raman scattering could not be completely suppressed. Table 1. Spectroscopic Data of Carborane-Appended Trimers

trimer

solvent

absorption maximum (nm)

control B 6 15 10 24 25 26

CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 H2O H2O H2O

290 290 294 307 290 294 300

a

emission maximum (nm)

rel area

360 360 370 360, 380 390 380 370

1.0 1.22 1.70 2.38 0.042 0.030 0.09

quantum yield (ΦF)

λc (nm)

E (eV)

0.27 0.33 0.46 0.86a 0.011 0.008 0.024

330 335 335 340 335 340 340

3.75 3.70 3.70 3.64 3.70 3.64 3.64

ΦF was calculated at OD290 ) 0.09.

Figure 4A and Table 1). The aqueous solution spectra of the water-soluble trimers 24-26 are shown in Figure 4B. The UV absorption of all the trimers, irrespective of the solvents used, showed absorption maxima close to 290 nm, except for the extended trimers 10 and 26, for which the absorbance maxima were red-shifted to 307 and 300 nm, respectively, due to the extended conjugation. Therefore, an excitation wavelength of 290 nm was chosen to measure emission intensities. A single emission maximum was observed for all trimers between 360 and 390 nm, except the extended trimer 10, for which weak vibrational splitting was observed at 360 and 380 nm. Trimers 6, 10, and 15 showed sharp emission intensities between 320 (20) (a) Finke, A. D.; Moore, J. F. Org. Lett. 2008, 10, 4851–4854. (b) He, Q.; Huang, H.; Yang, J.; Lin, H.; Bai, F. J. Mater. Chem. 2003, 13, 1085–1089. (c) Belser, P.; Zelewsky, A.; Frank, M.; Seel, C.; Vogtle, F.; Cola, L. D.; Barigelletti, F.; Balzani, V. J. Am. Chem. Soc. 1993, 115, 4076–4086. (d) Pang, J.; Marcotte, E. J.-P.; Seward, C.; Brown, R. S.; Wang, S. Angew. Chem., Int. Ed. 2001, 40, 4042– 4045. (e) Miller, T. M.; Neenan, T. X.; Zayas, R.; Bair, H. E. J. Am. Chem. Soc. 1992, 114, 1018–1025. (21) (a) Okumoto, K.; Shirota, Y. Chem. Mater. 2003, 15, 699–707. (b) Schmidt, B.; Rinke, M.; Gusten, H. J. Photochem. Photobiol. A: Chem. 1989, 49, 131–135. (22) Muller, M.; Kubel, C.; Mullen, K. Chem. Eur. J. 1998, 4, 2099–2109. J. AM. CHEM. SOC.

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and 470 nm (Figure 4A); less intense emissions were observed for the water-soluble trimers 24-26, over a wider wavelength range, between 320 and 550 nm (Figure 4B). However, all the trimers emit in the blue-violet region of the spectrum, as seen in Figure 4. In order to measure the relative fluorescence quantum yields, the samples were excited at 290 nm and were all prepared with OD290 ) 0.13. This allows for the emission intensities to be directly compared.23 Since the determination of absolute quantum yield is rather difficult, it is a common practice to determine the quantum yields of unknowns by comparing with a standard of known fluorescence quantum yield.24 The quantum yield of control B is reported to be 0.27.21b From the relative area under the fluorescence band and the quantum yield of the control B, the relative quantum yields (ΦF) of the carborane-appended trimers have also been calculated and are given in Table 1. The HOMO-LUMO gap energies were calculated using the Planck equation from the wavelengths where the absorbance and emission lines cross each other (λc) and are reported in electronvolts (eV) in Table 1. The incorporation of multiple o-carborane clusters in 6 and 15, containing three and six o-carborane clusters, respectively, led to about a 22% and 70% increase in their quantum yields in comparison to the carborane-unsubstituted control B. The combination of extended conjugation and the inclusion of o-carborane, as found in 10, resulted in a substantial enhancement (238%) of the quantum yield. Incorporation of o-carborane clusters also leads to a slight reduction of HOMO-LUMO gap energies (Table 1). Icosahedral carboranes are pseudoaromatic, and they also possess electron-withdrawing properties.7c,e The increase in quantum yields on the introduction of the o-carboranes into control B (see Table 1) is in sharp contrast to the recent observations of Kokado and co-workers, who found that the introduction of m-carboranes into the backbones of the extended π systems of p-phenyleneethynyl-like polymers resulted in polymers having intense blue emission in solution, while the introduction of o-carboranes in the extended π systems showed no luminescence but only aggregation-induced emission (AIE).25,26 An intensely blue emitting polymer was produced when p-carborane was introduced into the polymer backbone of a polyfluorene polymer.27 However, in our studies the aromatic conjugated core and o-carborane clusters are separated by a methylene moiety which effectively blocks π interactions by the carborane. Therefore, shifts in the absorption and emission maxima due to the extension of the aromatic system on the introduction of the o-carborane clusters are not observed. It seems much more likely that the size and three-dimensional structure of the o-carborane moieties serve to prevent π-π stacking interactions and also help to rigidify the system, minimizing nonradiative decay.28 Therefore, higher emission intensity was observed in all o-carborane-appended extended trimers. (23) Turro, N. J. Modern Molecular Photochemistry; Benjamin/Cummings: Menlo Park, CA, 1978. (24) Birks, J. B. Photophysics of Aromatic Molecules; Wiley: London, 1970. (25) (a) Kokado, K.; Tokoro, Y.; Chujo, Y. Macromolecules 2009, 42, 2925–2930. (b) Kokado, K.; Tokoro, Y.; Chujo, Y. Macromolecules 2009, 42, 9238–9242. (26) Kokado, K.; Chujo, Y. Macromolecules 2009, 42, 1418–1420. (27) Peterson, J. J.; Simon, Y. C.; Coughlin, B.; Carter, K. R. Chem. Commun. 2009, 4950–4952. (28) (a) Hong, Y.; Lam, J. W. Y.; Tang, B. Z. Chem. Commun. 2009, 4332– 4353. (b) We are also thankful to reviewers for valuable suggestions. 6582

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The aqueous solutions of the trimers 24 and 25, containing three and six nido-carboranes, respectively, showed much lower quantum yields, which were only about 3.4% and 1.8% of the values for the corresponding o-carborane-containing trimers (6 and 15) in dichloromethane. Thus, we found that a small number of monoanionic nido-carborane clusters induce good water solubility to 1,3,5-oligophenylene chromophores. When we increased the number of water solubility inducing nido-carborane anions from three in trimer 24 to six in trimer 25, we observed a decrease in ΦF of about 29%. Therefore, increasing the number of water solubility inducing charged nido-carborane clusters close to the chromophore diminishes the fluorescence quantum yield. The ΦF values of water-soluble trimers have been calculated by using the appropriate method, and only refractive index terms are considered during the calculation.29 Water-soluble fluorescent materials are used as fluorescent labels in biologically active probes.30 Thus, a number of other water-soluble chromophores are also available. Such chromophores carry hydrophilizing substituents such as sulfonic acid moieties,31 quaternary amine groups,32 polyethylene glycols,33 benzoate groups,34 and peptide chains35 attached to the aromatic chromophore scaffold. However, in most cases a very low fluorescence is observed in water.36 A chromophore that meets all the criteria, such as water solubility, high fluorescence intensity, nontoxicity, and high photostability, is rather difficult to find.36 The low fluorescence of chromophores in water may be attributed to a number of factors, such as the photoinduced electron transfer in polar solvents.29b,37,38 In addition, significant hydrogen bonding in water reduces ΦF by enhancing the nonradiative decay.29,37 However, in our case degassing the solvents to get rid of the quenching due to dissolved oxygen did not result in any noticeable change in the fluorescence intensity. Thermal Properties. Incorporation of carboranes enhances the thermal stability of the materials. Apart from a recent investigation in our laboratory,9 there have also been a number of literature reports on the enhancement of thermal stability due to the presence of carboranes,39 which motivated us to conduct a systematic thermal analysis of our trimers. TGA curves of (29) (a) Bigger, S. W.; Ghiggino, K. P.; Meilak, G. A.; Verity, B. J. Chem. Educ. 1992, 69, 675–677. (b) Barghouthi, S. A.; Perrault, J.; Holmes, L. H., Jr. Chem. Educ. 1998, 3, 1–10. (30) (a) Bastiaens, P. I. H.; Squire, A. Trends Cell Biol. 1999, 9, 48–52. (b) Nguyen, D. C.; Keller, R. A.; Jett, J. H.; Martin, J. C. Anal. Chem. 1987, 59, 2158–2161. (c) Peck, K.; Stryer, L.; Glazer, A. N.; Mathies, R. A. Proc. Natl. Acad. Sci. U.S.A. 1989, 86, 4087–4091. (31) (a) Jose, J.; Burgess, K. J. Org. Chem. 2006, 71, 7835–7839. (b) Rivas, B. L.; Maureira, A. Macromol. Symp. 2008, 270, 143–152. (32) (a) Schnurpfeil, G.; Stark, J.; Wohrle, D. Dyes Pigm. 1995, 27, 339– 350. (b) Knaus, S.; Gruber, H. F. J. Macromol. Sci. A, Pure Appl. Chem. 1996, 33, 869–881. (33) Patrick, M. J.; Ernst, L. A.; Waggoner, A. S.; Thai, D.; Tai, D.; Salama, G. Org. Biomol. Chem. 2007, 5, 3347–3353. Verma, S.; Padmawar, P. A.; Hauck, T.; Canteenwala, T.; Chiang, L. Y.; Pritzker, K. P. H. J. Macromol. Sci. A, Pure Appl. Chem. 2005, 42, 1497–1505. (34) (a) Biosselier, E.; Orneals, Catia.; Pianet, I.; Aranzaes, R. J.; Astruc, D. Chem. Eur. J. 2008, 14, 5577–5587. (35) (a) Klok, H.-A.; Hernandez, J. R.; Becker, S.; Mullen, K. J. Polym. Sci., Part A: Polym. Chem. 2001, 39, 1572–1583. (b) Stafforst, T.; Diederichsen, U. Eur. J. Org. Chem. 2007, 899–911. (c) Hempel, K.; Heinze, K. Chem. Eur. J. 2009, 15, 1346–1358. (36) (a) Kohl, C.; Weil, T.; Qu, J.; Mullen, K. Chem. Eur. J. 2004, 10, 5297–5310. (b) Quante, H.; Schlichting, P.; Rohr, U.; Geerts, Y.; Mullen, K. Macromol. Chem. Phys. 1996, 197, 4029–4044. (37) Lakowicz, J. R. Principles of Fluorescence Spectroscopy; Plenum Press: New York, 1986. (38) Lor, M.; Thielemans, J.; Viaene, L.; Cotlet, M.; Hofkens, J.; Weil, T.; Hampel, C.; Mullen, K.; Verhoeven, J. W.; Auweraer, M. V.; De Schryver, F. C. J. Am. Chem. Soc. 2002, 124, 9918–9925.

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Figure 5. (A) TGA curves of small trimers under nitrogen: (orange) 17; (green) 5; (red) 1; (blue) control A. (B) TGA curves of extended trimers under nitrogen: (green) 15; (red) 6; (blue) control B. Table 2. 10% Mass Loss Temperatures from TG Analysis trimer

temp (°C)

control A 1 5 17 control B 6 15

257 385 420 475 210 475 505

Figure 6. DSC analysis of small trimers at a heating rate of 5 K min-1: (A) control A; (T-5) 5; (T-17) 17; (T-23) 23.

small trimers are compared with that of control A (Figure 5A), and those of the extended trimers are compared with that of control B (Figure 5B). The temperatures at which 10% mass loss of all the trimers occurred have been summarized in Table 2. In general, for both the Bcage -and Ccage-appended trimers there was a dramatic enhancement of the thermal stability on incorporating the carborane. By analyzing the TGA plot shown in Figure 5A, we observe that the temperature at which 10% mass loss occurs for the control A is 257 °C, and then rapid decomposition of the compound was observed until complete degradation of the compound happened at about 320 °C. However, for 1, which contains three Bcage-appended o-carborane clusters, the point where 10% mass loss occurred is found to be 385 °C and finally about 47 wt % of the residue is maintained at 600 °C, whereas for 5, which contains three Ccage-appended o-carboranes, the 10% mass loss occurs at 420 °C and about 13 wt % of the residue is maintained at 600 °C. However, for 17, which has six Ccage-appended o-carboranes, the 10% mass loss observed at 475 °C and about 30 wt % of the residue is maintained at 600 °C. This was found to be the most stable compound in the smaller trimer series. A similar trend was observed for extended trimers, and these are even found to be more thermally stable than the smaller ones. For the extended control B the thermal degradation occurs in two successive steps. The first step, which occurs between 155 and 220 °C, accounts

for about 10% of the mass loss. This could be due to the decomposition of the peripheral phenyl ring. Then, in the second step rapid decomposition of the molecule was observed in the temperature range 380-500 °C and leads to almost 0 wt % residue. Such stepwise degradation is commonly observed in macromolecular and branched polymeric materials, where degradation starts from the branching units and loss of small molecular fragments also occurs.40 However, in the presence of peripheral o-carboranes such stepwise mass loss is not observed, and for both 6 and 15, about 51 wt % residue is maintained at 600 °C. The 10% mass loss temperature for 6 and 15 is also found to be high, occurring at 475 and 505 °C, respectively. Thus, we consistently found that increasing the number of o-carborane clusters increases the thermal stability of compounds. Another property of small Ccage-appended trimers was seen in their DSC thermograms (Figure 6). The phase transition temperatures of those trimers that have shown such mesomorphic behavior are summarized in Table 3. Only one endothermic peak is seen for the control A at 176.6 °C, whereas for 5, which contains three o-carborane clusters, we observe three endothermic peaks at 113.9, 160.3, and 372.5 °C, respectively. Similarly for 17, which contains six o-carborane clusters, endothermic peaks at 103.8, 146.3, and 388 °C were found. However, for the heptyl-substituted trimer

(39) (a) Hao, E.; Fabre, B.; Fronczeka, F. R.; Vicente, M. G. H. Chem. Commun. 2007, 4387–4389. (b) Benhabbour, S. R.; Parrott, M. C.; Gratton, S. E. A.; Adronov, A. Macromolecules 2007, 40, 5678–5688. (c) Farha, O. K.; Spokoyny, A. M.; Mulfort, K. L.; Hawthorne, M. F.; Mirkin, C. A.; Hupp, J. T. J. Am. Chem. Soc. 2007, 129, 12680– 12681.

(40) (a) Wriedt, M.; Sellmer, S.; Nather, C. Dalton Trans. 2009, 7975– 7984. (b) Kostler, S.; Zechner, B.; Trathnigg, B.; Fasl, H.; Kern, W.; Ribitsch, V. J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 1499– 1509. (c) Duquesne, S.; Bras, M. L.; Bourbogot, S.; Delobel, R.; Camino, G.; Eling, B.; Lindsay, C.; Roels, T.; Vezin, H. J. Appl. Polym. Sci. 2001, 82, 3262–3274. J. AM. CHEM. SOC.

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Table 3. DSC Data of Trimers trimer

peak (°C)

control A 5 17 23

176.6 113.9, 160.3, 372.5 103.8, 146.3, 388 115.3, 166.7

23 only two peaks at 115.3 and 166.7 °C are observed. The peaks observed at 372.5, 388, and 166.7 °C represent the melting of the respective trimers; the other peaks reflect solid-solid phase transitions. Substituted polycyclic aromatic hydrocarbons are known to form liquid-crystalline phases3,41 and in some cases such thermally induced solid-state phase transitions that are associated with the conformational reorganization of the bulky side groups.42 Unique properties such as molecular symmetry, conformational mobility, and their role in stabilizing liquid-crystalline phases make closocarborane clusters ideal choices for use in the synthesis of liquid-crystalline materials,43 and so the combination of π-conjugated systems and closo-carboranes therefore could be useful in making hybrid materials possessing such characteristics. Conclusion

In summary, we have demonstrated a silicon tetrachloride mediated facile synthetic route to symmetrical conjugated π systems containing multiple o-carborane clusters. The properties of carborane-containing π-conjugated compounds are found to be unique and significantly different from those of carboraneunsubstituted species. Presence of o-carborane clusters in π-conjugated systems prevents π-π stacking interactions and enhances the rigidity of such molecules. Thus, o-carboraneappended extended trimers show enhanced fluorescent intensity. Deboronation of o-carboranes led to the water-soluble compounds that are also found to be fluorescent in water but with a lower relative fluorescence quantum yield. The presence of o-carborane clusters also made these compounds highly thermally stable. An increase in the number of o-carborane clusters led to more thermally stable products. Thermally induced solid-solid phase transitions are observed in smaller Ccageappended trimers. Experimental Section General Methods. Reactions were generally performed under argon in oven-dried flasks. Solvents and reagents were added by syringes. Solvents were dried and distilled using standard procedures. Reagents were purchased and were used as received without further purification. All compounds were purified by column chromatography on silica gel (70-230 mesh, Aldrich). Yields of the products refer to analytically pure samples. 1H and 13C NMR spectra were recorded on a Bruker Fourier transform multinuclear NMR spectrometer at 500.13 and 125.75 MHz, respectively. Chemical shifts are reported relative to TMS (1H, δ 0.00 ppm), (41) (a) Rohr, U.; Schlichting, P.; Bohm, A.; Gross, M.; Meerholz, K.; Brauchhle, C.; Mullen, K. Angew. Chem., Int. Ed. 1998, 37, 1434– 1437. (b) Ito, S.; Wehmeier, M.; Brand, J. D.; Kubel, C.; Epsch, R.; Rabe, J. P.; Mullen, K. Chem. Eur. J. 2000, 6, 4327–4342. (42) Chen, J.; Anthony, J.; Martin, D. C. J. Phys. Chem. B 2006, 110, 16397–16403. (43) (a) Kaszynski, P.; Pakhomov, S.; Tesh, K. F.; Young, V. G., Jr. Inorg. Chem. 2001, 40, 6622–6631. (b) Nagamine, T.; Januszko, A.; Kaszynski, P.; Ohta, K.; Yasuyuki, E. J. Mater. Chem. 2006, 6, 3836– 3843. (c) Januszko, A.; Kaszynski, P.; Gruner, B. Inorg. Chem. 2007, 46, 6078–6082. (d) Kaszynski, P.; Douglas, A. G. J. Organomet. Chem. 1999, 581, 28–38. 6584

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and CDCl3 (13C, δ 77.0 ppm), and coupling constants are given in Hz. All 13C spectra are proton-decoupled. 11B NMR spectra were recorded at 64.2 MHz relative to BF3 · Et2O. Infrared spectra were recorded on an ATI Mattson Genesis series FT-IR spectrophotometer. Elemental analyses were carried out with a CHN-Analyzer 2400 (Perkin-Elmer). Melting points were measured with a MelTemp II apparatus (Laboratory Devices) and are uncorrected. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were performed on DSC 220C and TG/DTA 320 instrument (Seiko Instruments), respectively. UV absorption and emission spectra were measured with a Perkin-Elmer Lambda 19 UV-vis spectrometer and Hitachi F-2500 fluorescence spectrophotometer, respectively. Mass spectral analyses were performed with a Applied Biosystems Voyager-DE STR-MALDI-TOF spectrometer and Waters Q-TOF Ultima ES spectrometer. Preparations and Analytical Data of Compounds. Ketone 3. Compound 2 (710 mg, 1.89 mmol) was dissolved in 20 mL of solvent (THF/toluene, 1/1). Then 4-(acetylphenyl)boronic acid (622.1 mg, 3.79 mmol), PdCl2(PPh3)2 (53.26 mg, 4 mol %), and a solution of K2CO3 (785.35 mg, 5.69 mmol) in 5 mL of distilled water were added to the solution. The mixture was refluxed at 100 °C for 24 h and then extracted three times with dichloromethane, and the combined organic layers were dried over MgSO4. After evaporation of the solvent, the residue was purified by silica gel column chromatography with 5-25% ethyl acetate in hexanes as the eluent to obtain 520 mg of pure compound 3 as a colorless solid, yield 75%. Mp: 165 °C. 1H NMR (CDCl3, 500 MHz): δ 8.0 (d, 2H, J ) 7.96 Hz), 7.71 (d, 2H, J ) 7.98 Hz), 7.63 (d, 2H, J ) 7.75 Hz), 7.31 (d, 2H, J ) 7.79 Hz), 3.54 (s, 2H), 2.67 (s, 3H), 2.21 (s, 3H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 197.5, 144.8, 139.6, 136.1, 135.0, 130.9, 128.9, 127.4, 127.1, 77.3 (Ccage), 74.8 (Ccage), 40.7, 26.6, 23.6. 11B NMR (proton decoupled): -4.08, -5.47, -10.0. IR (KBr): 3034, 2589, 1678, 1602, 1365, 1266, 958, 817 cm-1. Anal. Calcd for C18H26B10O: C, 58.99; H, 7.15. Found: C, 59.08; H, 7.03. ES-MS (m/z): calcd 366.5, found 365.1 (M - 1, 100%). Ketone 4. Compound 2 (450 mg, 1.2 mmol) was dissolved in 10 mL of dry DMF. Then acetic anhydride (0.57 mL, 6 mmol), i-Pr2NEt (0.42 mL, 2.4 mmol), LiCl (255 mg, 6 mmol), and Pd2(dba)3 (22 mg, 2 mol %) were added to this solution. The mixture was then heated at 100 °C for 20 h, quenched with water, and extracted three times with diethyl ether. The combined organic layer was dried over MgSO4. After evaporation of the solvent the residue was purified by silica gel column chromatography with 5-15% ethyl acetate in hexane as eluent to obtain 250 mg of pure compound 4 as a colorless solid, yield 72%. Mp: 90 °C. 1H NMR (CDCl3, 500 MHz): δ 7.95 (d, 2H, J ) 6.85 Hz), 7.31 (d, 2H, J ) 6.85 Hz), 3.53 (s, 2H), 2.62 (s, 3H), 2.19 (s, 3H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 197.4, 139.9, 136.7, 130.6, 128.6, 76.6 (Ccage), 74.9 (Ccage), 40.9, 26.6, 23.6. 11B NMR (proton decoupled): -3.89, -5.50, -10.0. IR (KBr): 3005, 2944, 2599, 1673, 1608, 1417, 1359, 1271, 1020 cm-1. Anal. Calcd for C12H22B10O: C, 49.63; H, 7.64. Found: C, 49.61; H, 7.58. ES-MS (m/z): calcd 290.2, found 290.3 (M+). Ketone 9. Commercially available 4-(4-bromophenyl)acetophenone (8; 370.7 mg, 1.34 mmol) was dissolved in 40 mL of solvent (THF/toluene, 1/1). Then the carborane-appended boronic acid 716 (750 mg, 2.56 mmol), PdCl2(PPh3)2 (38 mg, 4 mol %), and a solution of K2CO3 (557.6 mg, 4.04 mmol) in 4 mL of distilled water were added to this solution. The reaction mixture was refluxed at 100 °C for 24 h and then quenched with water and extracted three times with dichloromethane. The combined organic layer was then dried over MgSO4. After evaporation of solvent the crude product was purified by silica gel column chromatography with 5-40% ethyl acetate in hexanes as the eluent to obtain 450 mg of the pure product 9 as a colorless solid, yield 75%. Mp: 240 °C. 1H NMR (CDCl3, 500 MHz): δ 8.0 (d, 2H, J ) 8.24 Hz), 7.77-7.72 (m, 6H), 7.65 (d, 2H, J ) 8.0 Hz), 7.31 (d, 2H, J ) 8.0 Hz), 3.54 (s, 2H), 2.67 (s, 3H), 2.22 (s, 3H, cluster-CH3). 13C NMR (CDCl3,

Carborane-Appended Symmetrical Extended π Systems

125 MHz): δ 197.6, 145.1, 140.2,140.1, 138.9, 136.0, 134.3, 130.8, 128.9, 127.7, 127.6, 127.1, 127.0, 77.5 (Ccage), 74.8 (Ccage), 40.9, 26.6, 23.7. 11B NMR (proton decoupled): -5.37, -9.99. IR (KBr): 3191, 2588, 1683, 1600, 1260, 1128, 809 cm-1. Anal. Calcd for C24H30B10O: C, 65.13; H, 6.83. Found: C, 65.0; H, 7.01. ES-MS (m/z): calcd 442.6, found 441.3 (M - 1, 100%). Carboranyl Adduct 13. 1-Methyl-o-carborane (2.49, 15.80 mmol) was dissolved in 120 mL of dry THF. This solution was cooled to 0 °C, and BuLi (10.36 mL, 1.6 M solution in hexane) was added dropwise to it. Then it was stirred at 0 °C for 1 h and then cooled to -10 °C. At -10 °C, LiI (307.5 mg, 2.29 mmol) and compound 12 (2.8 g, 7.18 mmol) in 10 mL of dry THF were added dropwise to the reaction mixture. Then the reaction mixture was stirred for 30 min at same temperature and warmed to room temperature for 24 h. After completion of the reaction, the reaction mixture was filtered off through a silica gel pad and concentrated. After evaporation of the solvent, the residue was purified by silica gel column chromatography with 5-10% ethyl acetate in hexanes as the eluent to obtain 2.5 mg of pure compound 13 as a colorless solid, yield 64%. Mp: 165 °C. 1H NMR (CDCl3, 500 MHz): δ 7.53 (s, 2H), 7.01 (s, 1H), 3.42 (s, 4H), 2.18 (s, 6H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 138.8, 137.3, 131.4, 94.1, 76.5 (Ccage), 74.8 (Ccage), 40.3, 23.6. 11B NMR (proton decoupled): -5.39, -9.96. IR (KBr): 2944, 2584, 1567, 1437, 1020 cm-1. Anal. Calcd for C14H33B20I: C, 30.88; H, 6.11. Found: C, 30.69; H, 6.08. Ketone 14. Compound 13 (300 mg, 0.55 mmol) was dissolved in 12 mL of solvent (THF/toluene, 1/1). Then 4-(acetylphenyl)boronic acid (180.6 mg, 1.101 mmol), PdCl2(PPh3)2 (15.4 mg, 4 mol %), and a solution of K2CO3 (228 mg, 1.65 mmol) in 2 mL of distilled water were added to the solution. The mixture was refluxed at 100 °C for 24 h and then extracted three times with dichloromethane, and the combined organic layer was dried over MgSO4. After evaporation of the solvent, the residue was purified by silica gel column chromatography with 40% ethyl acetate in hexanes as the eluent to obtain 270 mg of pure compound 14 as a colorless solid, yield 91%. Mp: 240 °C. 1H NMR (CDCl3, 500 MHz): δ 8.0 (d, 2H, J ) 7.8 Hz), 7.67 (d, 2H, J ) 7.8 Hz), 7.41 (s, 2H), 7.06 (s, 1H), 3.56 (s, 4H), 2.68 (s, 3H), 2.23 (s, 6H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 197.3, 144.3, 140.9, 136.5, 136.2, 131.6, 129.0, 128.9, 127.3, 74.9 (Ccage), 60.3 (Ccage), 41.1, 26.6, 23.6. 11B NMR (proton decoupled): -5.40, -9.94. IR (KBr): 2941, 2586, 1733, 1675, 1603, 1435, 1359, 1270, 1025, 957, 840 cm-1. Anal. Calcd for C22H40B20O: C, 49.23; H, 7.51. Found: C, 49.31; H, 7.54. ES-MS (m/z): calcd. 536.7, found: 536.6 (M+, 100%). Ketone 16. Compound 13 (490 mg, 0.9 mmol) was dissolved in 10 mL of dry DMF. Then acetic anhydride (0.43 mL, 4.5 mmol), i-Pr2NEt (0.32 mL, 1.8 mmol), LiCl (191 mg, 4.5 mmol), and Pd2(dba)3 (16.5 mg, 2 mol %) were added to the solution. It was heated at 100 °C for 20 h and then quenched with water, and the reaction mixture was extracted three times with diethyl ether. The combined organic layer was dried over MgSO4. After evaporation of the solvent the residue was purified by silica gel column chromatography with 30% ethyl acetate in hexane as eluent to obtain 400 mg of pure compound 16 as a colorless solid, yield 96%. Mp: 185 °C. 1H NMR (CDCl3, 500 MHz): δ 7.76 (s, 2H), 7.25 (s, 1H), 3.56 (s, 4H), 2.66 (s, 3H), 2.12 (s, 6H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 196.8, 137.8, 136.3, 136.2, 129.7, 76.5 (Ccage), 74.9 (Ccage), 40.8, 26.6, 23.7. 11B NMR (proton decoupled): -4.34, -8.93, -11.10. IR (KBr): 2944, 2585, 2351, 1703, 1603, 1448, 1360, 1293, 1210 cm-1. Anal. Calcd for C16H36B20O: C, 41.72; H, 7.88. Found: C, 41.67; H, 7.89. ES-MS (m/z): calcd 460.6764, found 461.5 (M+ + 1). Ketone 22. The TBDMS-protected o-carborane 18 was prepared as per the reported procedure.17 A solution of 18 (4 g, 15.48 mmol) in 60 mL of dry THF at 0 °C was treated with n-BuLi (1.6 M solution in hexane, 10.2 mL, 16.25 mmol). The solution was stirred at 0 °C for 30 min at room temperature. Then a solution of 1-iodoheptane (3.67 g, 16.25 mmol) in 5 mL of THF was added at 0 °C and the resulting reaction mixture was stirred at room

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temperature for 2 h and refluxed for 3 h. After removal of solvent the product was purified by silica gel column chromatography with 5-10% ethyl acetate in hexanes as the eluent to obtain a quantitative 5.5 g of pure compound 19 as an oil. 1H NMR (CDCl3, 500 MHz): δ 2.20-2.17 (m, 2H), 1.56-1.53 (m, 2H), 1.27 (br, s, 8H), 1.08 (s, 9H), 0.90 (br, s, 3H), 0.34 (s, 6H). 13C NMR (CDCl3, 125 MHz): δ 81.8, 76.2, 38.0, 31.5, 30.17, 29.16, 28.8, 27.57, 22.5, 20.3, 13.9, -2.4. Compound 19 (5.5 g, 15.42 mmol) was then solubilized in 40 mL of THF. It was cooled to -78 °C, and a 1 M solution of tetrabutylammonium fluoride in THF (32 mL, 32 mmol) was added to it at the same temperature over 10 min; this mixture was then warmed to room temperature and stirred at room temperature for 30 min. Water was added, and the reaction mixture was extracted with diethyl ether. Removal of the solvent and purification by column chromatography using hexane gave 3.5 g of the pure product 20 as a colorless oil, yield 94%. Compound 20 (600 mg, 2.475 mmol) was dissolved in 25 mL of DME, and to this solution was added n-BuLi (1.6 M solution in hexane, 1.7 mL, 2.72 mmol) at 0 °C. This mixture was then stirred at 0 °C for 1 h, and a solution of 4-iodobenzyl bromide (598 mg, 1.98 mmol) in 5 mL of dry DME was added to it at 0 °C; then it was refluxed at 90 °C for 24 h, after which the reaction mixture was cooled to room temperature and filtered over a silica gel pad. Removal of solvent and purification of the compound by silica gel column chromatography using hexane as the eluent resulted in 705 mg of pure compound 21 as an oily liquid, yield 62%. 1H NMR (CDCl3, 200 MHz): δ 7.72 (d, 2H, J ) 8.17), 6.97 (d, 2H, J ) 8.17), 3.41 (s, 2H), 2.29-2.19 (m, 2H), 1.59-1.48 (m, 2H), 1.29 (br, s, 8H), 0.94 (t, 3H). Compound 21 (130 mg, 0.282 mmol), Pd2(dba)3 (5.16 mg, 2 mol %), and LiCl (60 mg) were dissolved in 2 mL of dry DMF. Then acetic anhydride (0.13 mL, 1.414 mmol) and i-Pr2NEt (0.098 mL, 0.564 mmol) were added to this solution. The mixture was then stirred at 100 °C for 20 h. After this mixture was cooled to room temperature, it was filtered over a silica gel pad and then water was added. This mixture was then extracted with diethyl ether. The combined organic layer was dried with MgSO4. After evaporation of the solvent the residue was purified by column chromatography with 30% ethyl acetate in hexane to obtain 80 mg of pure product 22 as a colorless oil, yield 76%. 1H NMR (CDCl3, 500 MHz): δ 7.96 (d, 2H, J ) 8.15 Hz), 7.31 (d, 2H, J ) 8.15 Hz), 3.51 (s, 2H), 2.63 (s, 3H), 2.36-2.32 (m, 2H), 1.64-1.62 (m, 2H), 1.36-1.32 (m, 8H), 0.92 (t, 3H, J ) 7.0 Hz). 13C NMR (CDCl3, 125 MHz): δ 197.3, 140.0, 136.7, 130.6, 128.5, 80.1, 78.1, 40.6, 35.6, 31.6, 29.8, 29.2, 28.8, 26.6, 22.5, 14.0. 11B NMR (proton decoupled): -4.49, -10.25. IR (neat): 2957, 2928, 2856, 2580, 1685, 1609, 1264, 1012 cm-1. Anal. Calcd for C18H34B10O: C, 57.52; H, 9.15. Found: C, 57.50; H, 9.11. ES-MS (m/z): calcd 374.57, found 375.37 (M+ + 1). General Procedure for Trimerization of Ketones. Carboraneappended aryl ketones were dissolved in the required amounts of solvent (dry absolute ethanol/toluene, 1/1). Then SiCl4 was added to the solution and the reaction mixture was stirred at room temperature to 50 °C for 10-24 h. The reaction mixture was quenched with water and extracted three times with dichloromethane. The combined organic layer was dried with MgSO4. After evaporation of the solvent the crude product was purified by silica gel column chromatography. Trimer 5. Ketone 4 (170 mg, 0.58 mmol) was solubilized in 5 mL of solvent (absolute ethanol/toluene 3/1). Then SiCl4 (0.67 mL, 5.8 mmol) of was added to the solution at room temperature, and this mixture was then stirred at room temperature for 10 h. Purification of the compound with silica gel column chromatography with 5 -15% ethyl acetate in hexanes as eluent resulted in 120 mg of the pure product 5 as a colorless solid, yield 75%. Mp: >260 °C. 1H NMR (CDCl3, 500 MHz): δ 7.81 (s, 3H), 7.70 (d, 6H, J ) 8.0 Hz), 7.33 (d, 6H, J ) 8.0 Hz), 3.56 (s, 6H), 2.23 (s, 9H, clusterCH3). 13C NMR (CDCl3, 125 MHz): δ 141.6, 140.7, 134.4, 130.8, 127.5, 125.2, 77.5 (Ccage), 74.8 (Ccage), 40.9, 23.7. 11B NMR (proton decoupled): -5.43, -10.0. IR (KBr): 3033, 2925, 2853, 2581, 1598, J. AM. CHEM. SOC.

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1512, 1261, 1020, 810 cm-1. Anal. Calcd for C36H60B30: C, 52.91; H, 7.40. Found: C, 53.03; H, 7.33. MALDI-TOF-MS (m/z): calcd 817.19, found 817.78 (M+, 100%). Trimer 6. Ketone 3 (480 mg, 1.31 mmol) was dissolved in 24 mL of solvent (absolute ethanol/toluene, 3/1). Then SiCl4 (4.5 mL, 39.29 mmol) was added to the solution at room temperature, and this mixture was then stirred at 40 °C for 24 h. Purification of the compound with silica gel column chromatography with 5 -20% ethyl acetate in hexanes as eluent resulted in 280 mg of the pure product 6 as a colorless solid, yield 61%. Mp: >260 °C. 1H NMR (CDCl3, 500 MHz): δ 7.92 (s, 3H), 7.85 (d, 6H, J ) 8.10 Hz), 7.76 (d, 6H, J ) 8.10 Hz), 7.68 (d, 6H, J ) 8.0 Hz), 7.32 (d, 6H, J ) 8.0 Hz), 3.55 (s, 6H), 2.23 (s, 9H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 141.9, 140.3, 140.2, 139.6, 134.2, 130.8, 127.8, 127.5, 127.1, 125.0, 77.5 (Ccage), 74.8 (Ccage), 40.9, 23.7. 11 B NMR (proton decoupled): -5.45, -10.1. IR (KBr): 3029, 2580, 1589, 1504, 1387, 812 cm-1. Anal. Calcd for C54H72B30: C, 62.04; H, 6.94. Found: C, 62.11; H, 7.03. MALDI-TOF-MS (m/z): calcd 1045.47, found 1044.48 (M - 1, 100%). Trimer 10. Ketone 9 (410 mg, 0.926 mmol) was dissolved in 50 mL of solvent (absolute ethanol/toluene 3/1). Then SiCl4 (10.6 mL, 92.6 mmol) was added to the solution at room temperature, and this mixture was then stirred at 50 °C for 24 h. Purification of the compound with silica gel column chromatography with 5 -30% ethyl acetate in hexanes as eluent resulted in 118 mg of the pure product 10 as a colorless solid, yield 30%. Mp: >260 °C. 1H NMR (CDCl3, 500 MHz): δ 7.94 (s, 3H), 7.86 (d, 6H, J ) 8.0 Hz), 7.83-7.78 (m, 12H), 7.74 (d, 6H, J ) 8.0 Hz), 7.66 (d, 6H, J ) 7.7 Hz), 7.31 (d, 6H, J ) 7.7 Hz), 3.55 (s, 6H), 2.22 (s, 9H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 141.9, 140.3, 140.1, 139.8, 139.7, 139.3, 134.1, 130.8, 127.8, 127.5, 127.1, 125.0, 77.5 (Ccage), 74.8 (Ccage), 40.9, 23.7. 11B NMR (proton decoupled): -9.0, -11.25. IR (KBr): 3028, 2924, 2583, 1906, 1595, 1492, 819 cm-1. Anal. Calcd for C72H84B30: C, 67.89; H, 6.65. Found: C, 67.92; H, 6.63. MALDI-TOF-MS (m/ z): calcd 1273.76, found 1273.48 (M+, 100%). Trimer 15. Ketone 14 (260 mg, 0.484 mmol) was solubilized in 15 mL of solvent (absolute ethanol/toluene, 3/1). Then SiCl4 (2.8 mL, 24.2 mmol) was added to the solution at room temperature, and this mixture was then stirred at 45 °C for 24 h. Purification of the compound with silica gel column chromatography with 50% ethyl acetate in hexanes as eluent resulted in 100 mg of the pure product 15 as a colorless solid, yield 40%. Mp: >260 °C. 1H NMR (CDCl3, 500 MHz): δ 7.93 (s, 3H), 7.87 (d, 6H, J ) 7.2 Hz), 7.73 (d, 6H, J ) 7.2 Hz), 7.47 (s, 6H), 7.0 (s, 3H), 3.59 (s, 12H), 2.24 (s, 18H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 141.9, 141.6, 140.6, 139.3, 136.1, 130.9, 128.8, 127.9, 127.7, 125.2, 77.1 (Ccage), 74.9 (Ccage), 41.2, 23.7. 11B NMR (proton decoupled): -5.59, -9.95. IR (KBr): 3026, 2942, 2585, 1601, 1518, 1455, 1386, 1035, 830 cm-1. Anal. Calcd for C66H114B60: C, 50.94; H, 7.38. Found: C, 50.82; H, 7.20. MALDI-TOF-MS (m/z): calcd 1556.27, found 1555.46 (M+ - 1, 100%). Trimer 17. Ketone 16 (470 mg, 1.02 mmol) was dissolved in 40 mL of solvent (absolute ethanol/toluene, 3/1). Then SiCl4 (9.3 mL, 81.6 mmol) was added to the solution at room temperature, and this mixture was then stirred at 40 °C for 24 h. Purification of the compound with silica gel column chromatography with 20-25% ethyl acetate in hexanes as eluent resulted in 250 mg of the pure product 17 as a colorless solid, yield 55%. Mp: >260 °C. 1H NMR (CDCl3, 500 MHz): δ 7.74 (s, 3H), 7.52 (s, 6H), 7.11 (s, 3H), 3.60 (s, 12H), 2.24 (s, 18H, cluster-CH3). 13C NMR (CDCl3, 125 MHz): δ 141.4, 136.4, 131.4, 128.8, 125.5, 76.4 (Ccage), 75.0 (Ccage), 41.1, 23.7. 11B NMR (proton decoupled): -0.81, -5.21. IR (KBr): 2994, 2942, 2857, 2593 1593, 1449, 1387, 1328, 1027, 867 cm-1. Anal. Calcd for C48H102B60: C, 43.41; H, 7.74. Found: C, 43.46; H, 7.61. MALDI-TOF-MS (m/z): calcd 1327.98, found 1328.5 (M+ + 1, 100%). Trimer 23. Ketone 22 (80 mg, 0.213 mmol) was dissolved in 4 mL of dry absolute ethanol. The solution was cooled to 0 °C, 6586

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and then SiCl4 (0.49 mL, 4.27 mmol) was added to it. This mixture was then stirred at room temperature for 5 h. Then the reaction was quenched with water and the mixture extracted three times with dichloromethane. The combined organic layer was dried with MgSO4. After evaporation of the solvent the residue was purified by silica gel column chromatography using 20-25% ethyl acetate in hexane to obtain 40 mg of the pure product 23 as a colorless solid, yield 50%. 1H NMR (CDCl3, 500 MHz): δ 7.80 (s, 3H), 7.70 (d, 6H, J ) 8.0 Hz), 7.32 (d, 6H, J ) 8.0 Hz), 3.53 (s, 6H), 2.39-2.36 (m, 6H), 1.65-1.56 (m, 6H), 1.38-1.28 (m, 24H), 0.92 (t, 9H, J ) 7.0 Hz). 13C NMR (CDCl3, 125 MHz): δ 141.6, 140.6, 134.4, 130.8, 127.4, 125.2, 80.1, 79.0, 40.6, 35.6, 31.6, 29.8, 29.3, 28.9, 22.5, 14.0. 11B NMR (proton decoupled): -4.76, -10.0. IR (KBr): 2925, 2859, 2591, 1511, 1397, 1023, 808 cm-1. Anal. Calcd for C54H96B30: C, 60.63; H, 9.05. Found: C, 60.58; H, 9.11. MALDI-TOF-MS (m/z): calcd 1069.67, found 1069.68 (M+, 100%). General Procedure for Deboronation (Decapitation) of oCarborane Clusters Present in Trimers. NaOH was solubilized by stirring it in 5-10 mL of dry methanol. Then a solution of trimers in about 3-5 mL of THF was added to the solution and the reaction mixture was refluxed at 90 °C for 20 h. After that time the excess NaOH was neutralized by adding a few pieces of dry ice, and then the precipitate was filtered off over a frit. Evaporation of the solvent led to a white solid which was characterized without further purification. Decapitated Ttrimer 24. Trimer 6 (150 mg, 0.143 mmol) and NaOH (274 mg, 6.86 mmol) gave 140 mg of the colorless solid 24, which was water-soluble. Yield: 90%. Mp: > 260 °C. 1H NMR (CD3CN, 500 MHz): δ 8.05 (s, 3H), 7.98 (d, 6H, J ) 8.0 Hz), 7.85 (d, 6H, J ) 8.1 Hz), 7.7 (d, 6H, J ) 8.0 Hz), 7.45 (d, 6H, J ) 7.85 Hz), 3.31 (s, 6H), 2.18 (s, 9H, cluster-CH3), -2.4 (br, cluster-bridge 3H). 13C NMR (CD3CN, 125 MHz): δ 142.5, 142.0, 140.5, 139.4, 137.2, 129.2, 127.2, 126.9, 125.7, 124.0, 62.0 (br, Ccage), 54.6 (br, Ccage), 41.7, 21.8.11B NMR (proton decoupled): -9.4, -16.4, -19.8, -34.6, -36.7. IR (KBr): 2984, 2950, 2862, 2516 (B-H), 2014 (B-H-B), 1627, 1473, 1371, 1099, 825 cm-1. Anal. Calcd for C54H72B27Na3: C, 59.94; H, 6.71. Found: C, 59.89; H, 6.70. MALDI-TOF-MS (m/z): calcd 1082.01, found 1010.76 (M+ - 3Na - 3H). Decapitated Trimer 25. Trimer 15 (100 mg, 0.064 mmol) and NaOH (139 mg, 3.47 mmol) gave 90 mg of the colorless solid 25, which was water-soluble. Yield: 86%. Mp: > 260 °C. 1H NMR (CD3CN, 200 MHz): δ 8.13 (s, 3H), 8.07 (d, 2H, J ) 8.21), 7.91 (d, 2H, J ) 8.16), 7.59 (s, 3H), 7.17(s, 2H), 3.21 (s, 12H), 2.22 (s, 18H, cluster-CH3), -2.28 (br, cluster-bridge 6H). 13C NMR (CD3CN, 125 MHz): δ 143.5, 141.8, 141.2, 139.5, 139.1, 129.0, 127.9, 127.3, 124.7, 62.3 (br, Ccage), 54.8 (br, Ccage), 41.9, 22.3. 11 B NMR (proton decoupled): -9.4, -16.4, -19.7, -34.5, -36.7. IR (KBr): 3015, 2951, 2862, 2517 (B-H), 2013 (B-H-B), 1631, 1473, 1376, 1099 cm-1. Anal. Calcd for C66H114B54Na6: C, 48.65; H, 7.05. Found: C, 48.43; H, 7.22. MALDI-TOF-MS (m/z): calcd 1629.34, found 1537.62 (M+ - 4Na). Decapitated Trimer 26. Trimer 10 (140 mg, 0.11 mmol) and NaOH (211 mg, 5.2 mmol) gave 120 mg of the colorless solid 26, which was water-soluble. Yield: 83%. Mp: > 260 °C. 1H NMR (CD3CN, 500 MHz): δ 8.08 (s, 3H), 8.03-7.99 (m, 6H), 7.92-7.82 (m, 12H), 7.78-7.76 (m, 6H), 7.69-7.64 (m, 6H), 7.45-7.44 (m, 6H), 3.19 (s, 6H), 2.20 (s, 9H, cluster-CH3), -2.4 (br, cluster-bridge 3H). 13C NMR (CD3CN, 125 MHz): δ 142.8, 141.7, 140.1, 139.6, 138.6, 137.0, 129.3, 129.2, 127.3, 126.8, 125.6, 124.7, 61.4 (br, Ccage), 54.6 (br, Ccage), 41.7, 21.8. 11B NMR (proton decoupled): -9.7, -16.5, -19.8, -34.4, -36.4. IR (KBr): 2984, 2952, 2863, 2520 (B-H), 2002 (B-H-B), 1632, 1472, 1376, 1192, 1099 cm-1. Anal. Calcd for C72H84B27Na3: C, 66.00; H, 6.46. Found: C, 65.94; H, 6.42. MALDI-TOF-MS (m/z): calcd 1310.30, found 1216.62 (M+ - 3Na - 3BH).

Carborane-Appended Symmetrical Extended π Systems

Acknowledgment. We thank Michael Recchia for assistance during TGA and DSC studies. This work was supported by grants from the National Science Foundation (Nos. CHE-0906179 and CHE-0840504), the Robert A. Welch Foundation (No. N-1322), the Alexander von Humboldt Foundation and an NIU Inaugural Board of Trustees Professorship Award.

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Supporting Information Available: Text and figures giving synthetic procedures and characterization data for controls A and B and NMR spectra of the compounds prepared in this paper. This material is available free of charge via the Internet at http://pubs.acs.org. JA101845M

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